J. Phys. Chem.

A 2010, 114, 6613–6621 6613

Degradation of Atrazine by Electrochemical Advanced Oxidation Processes Using a

Boron-Doped Diamond Anode

Núria Borràs,† Ramon Oliver,† Conchita Arias,‡ and Enric Brillas*,‡

Unitat de Quı́mica Industrial, Escola UniVersitària d’Enginyeria Tècnica Industrial de Barcelona, UniVersitat
Politècnica de Catalunya, Comte d’Urgell 187, 08036 Barcelona, Spain, and Laboratori d’Electroquı́mica dels
Materials i del Medi Ambient, Departament de Quı́mica Fı́sica, UniVersitat de Barcelona, Martı́ i Franquès
1-11, 08028 Barcelona, Spain
ReceiVed: April 20, 2010; ReVised Manuscript ReceiVed: May 10, 2010

Solutions of 30 mg L-1 of the herbicide atrazine have been degraded by environmentally friendly
electrochemical advanced oxidation processes (EAOPs) such as anodic oxidation (AO), electro-Fenton (EF),
and photoelectro-Fenton (PEF) using a small open and cylindrical cell with a boron-doped diamond (BDD)
anode. AO has been carried out either with a stainless steel cathode or an O2 diffusion cathode able to generate
H2O2. Hydroxyl radicals (•OH) formed at the BDD surface in all EAOPs and in the bulk from Fenton’s
reaction between added Fe2+ and electrogenerated H2O2 in EF and PEF are the main oxidants. All treatments
yielded almost overall mineralization, although the rate for total organic carbon (TOC) removal is limited by
the oxidation of persistent byproducts with •OH at the BDD surface. In AO, TOC abatement is enhanced by
parallel electrochemical reduction of organics at the stainless steel cathode, while in PEF, it also increases
from additional photolysis of intermediates by UVA light under the synergistic action of •OH in the bulk.
The effect of current and pH on the degradative behavior of EAOPs has been examined to determine their
optimum values. Atrazine decay always follows a pseudo-first-order reaction, being more rapidly destroyed
from •OH in the bulk than at the BDD surface. Aromatic intermediates such as desethylatrazine,
desethyldesisopropylatrazine, and cyanuric acid and short linear carboxylic acids such as formic, oxalic, and
oxamic have been identified and quantified by reversed-phase and ion-exclusion HPLC, respectively. Released
inorganic ions such as Cl-, NO3-, and NH4+ have been followed by ionic chromatography.

1. Introduction found that boron-doped diamond (BDD) thin-film electrodes

Electrochemical advanced oxidation processes (EAOPs) are
environmentally friendly technologies that have recently re-
ceived increasing attention to mineralize persistent organic
pollutants (POPs) for water remediation.1-3 These techniques
are based on the electrogeneration of different kinds of hydroxyl
radicals (•OH), which is the second strongest oxidant known
after fluorine, with a high standard reduction potential (E°(•OH/
H2O) ) 2.80 V versus SHE). •OH can then nonselectively react
with POPs, giving dehydrogenated or hydroxylated derivatives
until total mineralization is achieved.
Electrochemical oxidation or anodic oxidation (AO) is the
most common EAOP for the treatment of wastewaters with low
organic contents.1,2,4-22 This method consists of the use of a
high O2 overvoltage anode (M) to oxidize the pollutants
contained in the electrolytic cell. When the applied current is
high enough, organics are mainly degraded by mediated
oxidation with a hydroxyl radical (M(•OH)) formed as an
intermediate of O2 evolution from water discharge2,4,5
are preferable for this technique, owing to their greater oxidation
ability than other conventional anodes such as PbO2,6,19 Ti/IrO2,6
RuO2,12 and Pt.11,16,20,21 BDD can completely mineralize many
aromatics and carboxylic acids4-21 because it possesses an inert
surface with low adsorption properties, remarkable corrosion
stability, and extremely wide potential windows in an aqueous
medium, giving rise to a very weak electrode-•OH interaction
that results in a higher O2 overvoltage than other anodes and
an enhancement of POP degradation with reactive BDD(•OH)
formed from reaction 1.
In an undivided cell, the mineralization power of AO can be
affected by the reduction of POPs on the cathode.2,3 This is not
feasible when a carbon polytetrafluoroethylene (PTFE) O2
diffusion cathode is utilized since it mainly supplies continuously
H2O2 to the contaminated solution from the two-electron
reduction of O2 gas directly injected into it16,20

M + H2O f M(•OH) + H+ + e- (1) O2(g) + 2H+ + 2e- f H2O2 (2)

The oxidation power of AO depends on the reactivity of M(•OH)

species generated at the anode surface. Recently, it has been This method is called AO with electrogenerated H2O2 (AO-
H2O2) and involves the degradation of POPs by different species
* To whom correspondence should be addressed. Tel: +34 934021223. such as M(•OH) and other weaker oxidizing agents like H2O2
Fax: +34 934021231. E-mail: brillas@ub.edu.
†
Universitat Politècnica de Catalunya. and a hydroperoxyl radical (HO2•) produced from its oxidation
‡
Universitat de Barcelona. at the anode3,11
10.1021/jp1035647  2010 American Chemical Society
Published on Web 05/27/2010
6614 J. Phys. Chem. A, Vol. 114, No. 24, 2010
H2O2 f HO•2 + H+ + e- (3)
The oxidation power of electrogenerated H2O2 can be
enhanced by the electro-Fenton (EF) method.3,16,20,23-33 This
EAOP consists of the addition of a small amount of catalytic
Fe2+ to the acidic contaminated solution to react with hydrogen
peroxide generating •OH and Fe3+ in the bulk from Fenton’s
reaction34
Fe2+ + H2O2 f Fe3+ + •OH + OH- (4)
Typical cathodes for EF are carbon-felt25,28-33 and O2 diffu-
sion16,20,23,26-28 electrodes allowing an efficient O2 reduction from
reaction 2. An advantage of this procedure is the regeneration
of Fe2+ from the cathodic reduction of Fe3+, thereby promoting
reaction 4 and favoring the continuous production of oxidant
•
OH for POPs destruction.28,29
A variant of the EF process is photoelectro-Fenton (PEF),
where the contaminated solution is irradiated by an UVA light
of λmax ) 360 nm,16,20,23,26,27 which photolyzes the Fe(OH)2+
complex, the predominant species of Fe3+ in the pH range of
2.5-5.0, as follows34,35
Fe(OH)2+ + hν f Fe2+ + •OH (5)
In PEF, a greater amount of •OH is directly formed from reaction
5, and also, a greater quantity of Fe2+ is regenerated to accelerate
Fenton’s reaction 4. Moreover, complexes between Fe(III) and
the intermediates can be rapidly photodecomposed, increasing
the oxidation ability of this method.
Atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-tri-
azine) has been the most widely used pre- and postemergency
herbicide in the world for combating grassy and broadleaf weeds
in sorghum, corn, rangeland, and sugar cane. This compound
has a low solubility of near 34 mg L-1 at 20 °C in neutral
aqueous medium and has been found in ground and surface
waters because its half-life is as long as about 100 days.22,33 Its
presence in the aquatic environment is a potential danger for
public health since it is considered an endocrine disruptor.36
For this reason, atrazine belongs to the priority list of 76
substances of the Water Framework of the Directive 2000/60/
EC of the European Parliament, and it has been banned in
several countries,37 although its presence and that of its
metabolites in natural waters will continue to last for several
years.33
Many research efforts have been made to develop potent and
environmentally friendly techniques for atrazine removal from
aqueous media. The degradation of this POP has been studied
by biological methods,38,39 chemical and photochemical pro-
cesses,40 photodegradation,41 and chemical, photochemical, and
photocatalytic advanced oxidation processes (AOPs) with •OH
generation including O3/H2O2,42 TiO2/UV,43-47 H2O2/UV,48,49
H2O2/Fe2+,49,50 and H2O2/Fe2+/UV or H2O2/Fe3+/UV.49,51 How-
ever, no total mineralization of atrazine is reached using the
above methods since cyanuric acid (2,4,6-trihydroxy-1,3,5-
triazine) is detected as the predominant byproduct, along with
other substituted triazines. The same behavior has been reported
by several EAOPs. Thus, AO with a Pt anode only allows the
conversion of atrazine to cyanuric acid without any formation
of CO2.22 In contrast, the latter persistent compound can be
mineralized by AO using an undivided cell with a BDD anode
and a stainless steel (SS) cathode,9 occurring more rapidly with
Borràs et al.
increasing current and pH, although saturated solutions of
atrazine only undergo about 70 and 90% total organic carbon
(TOC) decay operating in acid and neutral media at 50 mA
cm-2, respectively, without overall removal of cyanuric acid.
No better results have been described by applying EF to treat
250 mL of a 42 mg L-1 atrazine solution with 0.1 mM Fe3+
(pH 3) as the catalyst using an undivided cell with a carbon-
felt cathode since at 250 mA, 63% TOC decay was found with
a Pt anode, which raised to 82% with a BDD anode.33 More
research is then required to show if this POP can be efficiently
mineralized by EAOPs with a BDD anode.
This paper reports a comparative study on the degradation
of 30 mg L-1 atrazine solutions by AO, EF, and PEF with an
undivided cell containing a BDD anode in order to clarify the
oxidative action of the different hydroxyl radicals produced in
these EAOPs. The former technique was tested with a stainless
steel (AO-SS) or O2 diffusion (AO-H2O2) cathode to ascertain
if electrochemical reduction can affect the degradative process.
The effect of applied current and pH on the degradation power
of each method was examined. The decay of the herbicide and
the evolution of its byproducts, with special attention for
cyanuric acid as the most persistent aromatic, were determined
by chromatographic techniques.
2. Experimental Section
2.1. Chemicals. Atrazine and five of its possible primary
byproducts22,33 such as desethylatrazine, desisopropylatrazine,
desethyldesisopropylatrazine, desethyldesisopropyl-2-hydroxyatra-
zine, and cyanuric acid were reagent-grade supplied by Sigma.
Formic, oxalic, and oxamic acids were reagent-grade purchased
from Panreac. Sulfuric acid, anhydrous sodium sulfate, ferrous
sulfate heptahydrate, and sodium hydroxide were analytical-
grade from Merck and Fluka. Solutions were prepared with high-
purity water obtained from a Millipore Milli-Q system with
resistivity > 18 MΩ cm at 25 °C. Organic solvents and other
chemicals used were either HPLC or analytical-grade supplied
by Aldrich, Lancaster, Merck, and Panreac.
2.2. Electrolytic Systems. All electrolyses were conducted
in an open and undivided cylindrical cell containing 100 mL
of solution stirred with a magnetic bar at 800 rpm to ensure its
homogenization and the transport of reactants toward/from the
electrodes. The solution temperature was regulated at 35 °C by
circulating external thermostatted water through the double
jacket of the cell. The anode was a BDD thin-film electrode
provided by Adamant Technologies (La-Chaux-de-Fonds, Swit-
zerland) and synthesized by the hot filament chemical vapor
deposition technique on single-crystal p-type Si(100) wafers (0.1
Ω cm, Siltronix). Before its use in the electrolytic assays, it
was polarized for 60 min in a 0.05 M Na2SO4 solution at 300
mA to remove the impurities of its surface. The cathode was
either a stainless steel (AISI 304 grade) sheet for AO-SS or a
carbon-PTFE from E-TEK (Somerset, NJ, USA) for AO-H2O2,
EF, and PEF. The preparation of the latter cathode is described
elsewhere,23 and it was fed with pure O2 at 12 mL min-1 for
continuous H2O2 generation from reaction 2. The geometric area
of all electrodes in contact with the solution was 3 cm2, and
the interelectrode gap was about 1 cm. PEF trials were made
under irradiation with a Philips TL/6W/08 fluorescent black light
blue tube of λmax ) 360 nm, placed at the top of the open cell
at 7 cm above the solution. It yielded a photoionization energy
input of 1.4 W m-2, as detected with a NRC 820 laser power
meter.
Comparative degradations of 100 mL of solutions containing
30 mg L-1 of atrazine in 0.05 M Na2SO4 were performed with
Degradation of Atrazine by EAOPs
AO-SS, AO-H2O2, EF, and PEF. The influence of constant
applied current between 100 and 450 mA and pH in the range
of 2.0-7.0 on the oxidation power of each process was
examined. In EF and PEF, 0.5 mM Fe2+ was employed as the
catalyst since this content was found optimal for analogous
treatments of aromatic pollutants.3
2.3. Apparatus and Product Analysis Procedures. The
solution pH was measured with a Crison GLP 22 pH meter.
Electrolyses were performed with an Amel 2053 potentiostat-
galvanostat. Prior to analysis of aliquots withdrawn from
electrolyzed solutions, they were filtered with 0.45 µm PTFE
filters from Whatman. The solution TOC was determined with
a Shimadzu VCSN total organic carbon analyzer. Reproducible
TOC values with an accuracy of (1% were found by injecting
50 µL aliquots into the analyzer. These data allowed estimating
the mineralization current efficiency (MCE, in %) for each
treated solution at a given time t (h) by the equation16,20
nFVs∆(TOC)exp
MCE ) × 100 (6)
4.32 × 107mIt
where F is the Faraday constant (96487 C mol-1), Vs is the
solution volume (L), ∆(TOC)exp is the solution TOC decay (mg
L-1), 4.32 × 107 is a conversion factor to homogenize units
(3600 s h-1 × 12000 mg mol-1), m is the number of carbon
atoms of atrazine (eight C atoms), and I is the applied current
(A). The number of electrons (n) consumed per atrazine
molecule was taken as 70, assuming that it is mineralized to
CO2 with the release of Cl- and NO3- as the main primary
ions, as will be discussed below. This total process can be
written according to the following reaction
C8H14ClN5 + 31H2O f 8CO2 + Cl- + 5NO-
3 +
76H+ + 70e- (7)
Atrazine decay and the evolution of its aromatic byproducts
were followed by reversed-phase HPLC using a Waters 600
liquid chromatograph fitted with a Spherisorb ODS 5 µm, 150
mm × 4.6 mm (i.d.), column at room temperature, coupled with
a Waters 996 photodiode array detector selected at λ ) 280
nm. Carboxylic acids were detected by ion-exclusion HPLC
using the above liquid chromatograph fitted with a Bio-Rad
Aminex HPX 87H, 300 mm × 7.8 mm (i.d.), column at 35 °C
and the photodiode array detector selected at λ ) 210 nm. In
all HPLC measurements, 20 µL aliquots were injected into the
chromatograph. The mobile phase was a 40:60 (v/v) acetonitrile/
water mixture at 0.8 mL min-1 and 4 mM H2SO4 at 0.6 mL
min-1 for reversed-phase and ion-exclusion HPLC, respectively.
Inorganic ions were quantified by ionic chromatography with a
Shimadzu 10 Avp HPLC coupled with a Shimadzu CDD 10
Avp conductivity detector by injecting 25 µL aliquots. A Shodex
IC YK-421, 125 mm × 4.6 mm (i.d.), cation column under
circulation of a mobile phase composed of 5.0 mM tartaric acid,
2.0 mM dipicolinic acid, 24.2 mM boric acid, and 15.0 mM
corona ether at 1.0 mL min-1 and 40 °C was employed to
quantify the NH4+ ion at a retention time (tr) of 5.0 min. A
Shim-Pack IC-A1S, 100 mm × 4.6 mm (i.d.), anion column
and 1.0 mM p-hydroxybenzoic acid and 1.1 mM N,N-diethyl-
ethanolamine of pH ) 7.9 as the mobile phase at 1.5 mL min-1
and 40 °C were used for the measurements of Cl- (tr ) 3.2
min) and NO3- (tr ) 7.2 min) contents.
J. Phys. Chem. A, Vol. 114, No. 24, 2010 6615
Figure 1. TOC removal with consumed specific charge for the
degradation of 100 mL of a 30 mg L-1 atrazine solution in 0.05 M
Na2SO4 of pH 3.0 using an open and undivided cylindrical cell with a
3 cm2 boron-doped diamond (BDD) anode at 300 mA and 35 °C. (0)
Anodic oxidation with a 3 cm2 stainless steel cathode (AO-SS). The
other three methods used a 3 cm2 O2 diffusion cathode: (O) anodic
oxidation with electrogenerated H2O2 (AO-H2O2), (b) electro-Fenton
with 0.5 mM Fe2+ (EF), and (2) photoelectro-Fenton with 0.5 mM
Fe2+ under 6 W UVA irradiation of λmax ) 360 nm (PEF).
3. Results and Discussion
3.1. Comparative Degradation by EAOPs. To clarify the
oxidation power of the different methods tested, a first series
of trials was made by electrolyzing 30 mg L-1 atrazine solutions
(corresponding to 13.4 mg L-1 TOC) in 0.05 M Na2SO4 of pH
3.0 at 300 mA (current density, 100 mA cm-2). In all cases,
the solution remained colorless, and its pH decreased to 2.6-2.8
at the end of 360 min of electrolysis. The TOC removal against
consumed specific charge (Q, in Ah L-1) obtained for these
experiments is depicted in Figure 1. A gradual decay of TOC
can always be observed up to 12 Ah L-1 (240 min), whereupon
the solution becomes hardly degraded, attaining 90-92% of
final decontamination. That means that almost total mineraliza-
tion can only be reached for all EAOPs because of the formation
of very stable byproducts in small extent (10% as the maximum)
that cannot be destroyed under the action of electrogenerated
oxidants, direct electron transfer at the BDD anode, and/or direct
electrochemical reduction at the SS cathode.
Results of Figure 1 also evidence that the degradation ability
of EAOPs tested follows the sequence AO-H2O2 ≈ EF < AO-
SS ≈ PEF. This trend is rather surprising if one takes into
account that previous work on aromatic pollutants reports a
faster degradation by EF than that by AO, which is even strongly
increased using PEF.3,16,20,26-28 The similar degradation rate
obtained for the AO-H2O2 and EF treatments of the heteroaro-
matic atrazine can then be related to the persistent nature of
most byproducts that are mineralized by BDD(•OH) formed from
reaction 1 but not with •OH produced by Fenton’s reaction 4.
Partial electro-oxidation of atrazine and its intermediates (e.g.,
cyanuric acid) by direct electron transfer at the BDD anode is
also possible.2,3 This behavior also discards a significant
participation in the degradation process of weaker oxidants such
as H2O2 electrogenerated by reaction 2 and HO2• formed from
reaction 3, as well as other produced oxidizing agents at the
BDD anode such as the peroxodisulfate ion (S2O82-) by reaction
8 and ozone by reaction 9.2,5
-
4 f S2O8 + 2e
2SO2- 2-
(8)
6616 J. Phys. Chem. A, Vol. 114, No. 24, 2010 Borràs et al.

3H2O f O3(g) + 6H+ + 6e- (9) 2•OH f H2O2 (11)

The fact that AO-SS is slightly more potent than AO-H2O2 can H2O2 + •OH f HO2• + H2O (12)
be explained by the parallel direct electrochemical reduction
of some intermediates at the SS cathode giving species that are
more easily destroyed and mineralized with BDD(•OH). As can Fe2+ + •OH f Fe3+ + OH- (13)
be seen in Figure 1, the maximum difference between these
methods is reached at 4.5 Ah L-1 (90 min), with TOC removals The action of these side reactions can be more clearly
of 57% for AO-SS and 40% for AO-H2O2. On the other hand, observed in Figure 2b for AO-H2O2 and PEF treatments, where
the superiority of the PEF process compared with EF and AO- the corresponding TOC decay against Q at 450 mA is much
H2O2 can be due to the additional photodecomposition of some slower than those found at 100 and 300 mA. That means that
intermediates that enhances the mineralization of the organic increasing the current from 300 to 450 mA causes a larger
matter. This point will be more extensively discussed below consumption of the applied specific charge by the acceleration
from the detection and quantification of the main stable of waste reactions like reactions 8-13, giving a relatively lower
byproducts. Note that the small mineralization action of •OH quantity of organic oxidation events. This phenomenon is also
during EF is also indicative of little influence of the greater associated with a loss in efficiency of processes.
production of this radical from reaction 5 on the oxidation power Figure 2c depicts the mineralization current efficiency
of PEF. calculated from eq 6 versus Q for the experiments of Figure
3.2. Effect of Current and pH on the Degradation Rate
and Mineralization Current Efficiency. The applied current
is an important experimental parameter that can affect the
oxidation ability of EAOPs tested.2,3 To check this possibility,
comparative degradation of 30 mg L-1 atrazine solutions at pH
3.0 were made for AO-SS, AO-H2O2, EF, and PEF at 100, 300,
and 450 mA. Figure 2a and b exemplifies the corresponding
TOC decay with electrolysis time and specific charge, respec-
tively, in the case of AO-H2O2 and PEF treatments. At 100 mA,
a quite similar and slow degradation rate can be observed in
Figure 2a for both methods, reaching close to 85% TOC removal
at 540 min of electrolysis. Similar TOC trends were found for
the AO-SS and EF techniques at this current. This behavior
indicates that the mineralization process of all EAOPs at 100
mA is limited by the slow destruction of very persistent
intermediates with BDD(•OH), without any significant participa-
tion of other electrogenerated oxidants and/or reduction pro-
cesses. Figure 2a shows a high increase in TOC removal when
the current rises from 100 to 300 mA, attaining ∼90-92%
mineralization in 360 min, as expected from the concomitant
production of a greater amount of BDD(•OH) that oxidizes much
more rapidly the limiting persistent byproduct. At 300 mA, a
greater generation of •OH from reactions 4 and/or 5 also takes
place because of the electrogeneration of greater H2O2
concentration.11,26 This can produce higher contents of species
that can be photodecomposed by UVA light, thus explaining
the slightly higher oxidation power of PEF than that of AO-
H2O2 and EF under these conditions (see Figures 1 and 2a).
Compared with 100 mA, the larger acceleration of the electro-
chemical reduction of some byproducts on the SS cathode at
300 mA can be accounted for by the quicker TOC removal for
AO-SS than that for AO-H2O2 at this current (see Figure 1). In
contrast, when 450 mA is applied, only a slight increase in the
degradation rate with respect to that for 300 mA is found in all
cases (see Figure 2a), indicating that the process is controlled
by mass transfer of persistent byproducts toward the anode.
Then, the excess of current is consumed in parasitic reactions
of hydroxyl radicals involving mainly the anodic oxidation
of BDD(•OH) to O2 via reaction 10 and the dimerization of
•
OH to H2O2 by reaction 11 or its destruction with H2O2 and
Fe2+ from reactions 12 and 13, respectively,2,3 as well as in Figure 2. Effect of applied current on TOC abatement with (a)
the production of more S2O82- from reaction 8 and O3 from electrolysis time and (b) consumed specific charge for the degrada-
tion of 100 mL of a 30 mg L-1 atrazine solution in 0.05 M Na2SO4
reaction 9. of pH 3.0 at 35 °C by (4, O, 3) AO-H2O2 and ([, 2, 1) PEF.
Current: (4, [) 100 mA, (O, 2) 300 mA, and (3, 1) 450 mA. Plot
(c) gives the corresponding mineralization current efficiency cal-
2BDD(•OH) f 2BDD + O2(g) + 2H+ + 2e- (10) culated from eq 6.
Degradation of Atrazine by EAOPs
Figure 3. Effect of pH on TOC removal for the degradation of 100
mL of a 30 mg L-1 atrazine solution in 0.05 M Na2SO4 at 300 mA and
35 °C using (a) AO-H2O2 and (b) PEF. Solution pH: (3, b) 2.0,
(O, 2) 3.0, (9) 4.0, (0, 1) 6.0, and ([) 7.0. In the three latter media,
the pH was continuously adjusted to its initial value by adding small
volumes of 0.05 M NaOH.
2b. Low MCE values are reached for atrazine degradation
because of the slow reaction of its intermediates with electro-
generated oxidants. Decreasing maximum efficiencies of 3.0,
2.5, and 2.0% with increasing currents of 100, 300, and 450
mA can be seen at the first stages of AO-H2O2. Under these
conditions, maximum efficiencies of 3.1, 3.1, and 2.0% are
determined for PEF. These trends agree with the formation of
smaller relative amounts of oxidants like BDD(•OH) and •OH
with raising current because of the concomitant acceleration of
waste reactions. The existence of a maximum value for MCE
is indicative of a fast conversion to CO2 of several byproducts
at short electrolysis time and the parallel formation of persistent
intermediates that are slowly destroyed at longer time. Moreover,
the presence of less organic matter in solution with prolonging
electrolysis also causes a drop in efficiency.2
The above results indicate that a current of 300 mA (current
density 100 mA cm-2) is optimal for atrazine degradation since
it allows reaching of the higher degradation rate with an
efficiency similar to that of lower currents. This current was
then used to investigate the influence of solution pH in the range
of 2.0-7.0 on all processes. Solutions starting from pH > 4.0
were quickly acidified during electrolysis, and for this reason,
these trials were made with continuous pH regulation to their
initial value by adding 0.05 M NaOH. In contrast, the treatments
for initial pH 2.0 and 3.0 were carried out without pH regulation
because the solution pH dropped slowly to final values of 1.9
and 2.7. Figure 3a illustrates the small effect of the pH on the
degradation of atrazine in AO-H2O. Similar TOC-Q plots can
be observed for pH 2.0 and 3.0, while slightly smaller TOC
decay takes place at pH 6.0, although in all cases, about 85%
mineralization is already attained at 12 Ah L-1 (240 min). This
slight deceleration in TOC removal at pH 6.0 can be associated
with the formation of byproducts that react more slowly with
BDD(•OH) since the concentration of this electrogenerated
J. Phys. Chem. A, Vol. 114, No. 24, 2010 6617
species is expected to be pH-independent.2,8,11 The same
behavior was obtained for the AO-SS and EF processes. A more
significant influence of pH can be seen in Figure 3b for the
PEF treatment, where TOC undergoes an analogous abatement
starting from pH 2.0 and 3.0, which is progressively lower as
the pH raises from 3.0 to 7.0. For example, mineralization
degrees of 80% at pH 2.0, 77% at pH 3.0, 63% at pH 4.0, 53%
at pH 6.0, and 50% at pH 7.0 are determined at 6 Ah L-1 (120
min). This tendency can be related to the gradual smaller
production of •OH from Fenton’s reaction 4, which is maximum
at pH 2.8.34 Although this radical does not act as the limiting
oxidizing species, it can favor the generation of intermediates
that can be photodecomposed by UVA light in PEF, thereby
enhancing the oxidation power of this method compared with
that of AO-H2O2 and EF (see Figure 1). Evidence on this action
of the •OH radical will be discussed below. Accordingly, the
decay in •OH concentration with increasing pH leads to lower
amounts of byproducts that can be photolyzed, decreasing the
degradation rate of the process. Figure 3b also shows that about
92-94% mineralization was reached for all PEF treatments at
18 Ah L-1, indicating that about 6-8% of the persistent
intermediates cannot be destroyed by this method. Results of
Figure 3a and b allow one to establish that pH values of 2.0-3.0
are optimal for the treatment of atrazine solutions by EAOPs
with a BDD anode.
3.3. Kinetics for Atrazine Decay. The role of electrogen-
erated oxidants such as BDD(•OH) and •OH in the destruction
of atrazine was analyzed by reversed-phase HPLC, where it
displayed a well-defined absorption peak at tr ) 7.4 min. Blank
experiments performed at pH 3.0 with and without 20 mM H2O2
under UVA irradiation did not show any significant removal of
the herbicide. This indicates that it is not directly photolyzed
and can only be attacked by the different hydroxyl radicals
generated in the EAOPs.
Figure 4a shows the abatement of atrazine concentration at
the optimum pH 3.0 and 100 mA for all methods tested. The
herbicide is removed at a similar rate for AO-SS and AO-H2O2,
to disappear from solution in 100 min, as expected if it is only
attacked by BDD(•OH) formed from reaction 1 under these
conditions. A much faster and quite analogous disappearance
of atrazine takes place for EF and PEF, with overall removal in
only 40 min. The enhancement of atrazine destruction in the
two latter EAOPs can be accounted for by its parallel reaction
with •OH produced from Fenton’s reaction 4. The similar rate
for atrazine decay in EF and PEF is indicative of little
participation of photocatalytic reaction 5 in •OH generation and
corroborates that it is not directly photolyzed by UVA light, as
pointed out above from the blank experiments. These findings
evidence that •OH is able to rapidly oxidize heteroaromatics,
although this radical is so inefficient to destroy some persistent
byproducts that it plays a very poor role in the total mineraliza-
tion process (see Figure 1).
The above concentration decays were fitted to kinetic
equations with different simple reaction orders. Excellent linear
correlations were only obtained considering a pseudo-first-order
reaction, as can be seen in the inset panel of Figure 4a. From
this analysis, a pseudo-first-order rate constant (k1) of 6.4 ×
10-4 s-1 (square regression coefficient (R2) ) 0.982) for AO-
SS and 6.1 × 10-4 s-1 (R2 ) 0.980) for AO-H2O2 was found,
suggesting a constant production of BDD(•OH) from reaction
1. The apparent rate constant increases ∼3.6 times for EF, k1
) 2.3 × 10-3 s-1 (R2 ) 0.992), and PEF, k1 ) 2.2 × 10-3 s-1
6618 J. Phys. Chem. A, Vol. 114, No. 24, 2010
Figure 4. Decay of atrazine concentration with electrolysis time during
the treatment of 100 mL of a 30 mg L-1 herbicide solution in 0.05 M
Na2SO4 of pH 3.0 at 35 °C. In plot (a), (]) AO-SS, (O) AO-H2O2, (b)
EF, and (3) PEF at 100 mA. In plot (b), AO-SS at (]) 100, (0) 300,
and (4) 450 mA. Each inset panel presents the corresponding kinetic
analysis, assuming that atrazine disappears following a pseudo-first-
order reaction.
(R2 ) 0.996), indicating that atrazine reacts more quickly with
•
OH, which is also generated at a constant rate from Fenton’s
reaction 4.
The influence of applied current on atrazine decay for the
AO-SS method was also examined. Results of Figure 4b show
that the herbicide abatement is strongly accelerated as the current
rises, disappearing in shorter times of 100, 25, and 15 min at
increasing 100, 300, and 450 mA. The inset panel of Figure 4b
depicts the good straight lines obtained considering a pseudo-
first-order reaction, leading to a k1 value of 6.4 × 10-4 s-1 (R2
) 0.982) at 100 mA, 2.8 × 10-3 s-1 (R2 ) 0.980) at 300 mA,
and 4.9 × 10-3 s-1 (R2 ) 0.982) at 450 mA. Compared with
100 mA, the rate constant rises 4.4 and 7.6 times, while the
current only increases 3 and 4.5 times for 300 and 450 mA,
respectively. This larger enhancement in k1 cannot be related
to the concomitant production of more oxidant BDD(•OH),
which is expected to increase to a lesser extent than the ratio of
currents, as pointed out above. This suggests the existence of
parallel electrochemical reduction of atrazine at the SS cathode
that takes place to a larger extent as the current rises from 100
mA, in agreement with the faster TOC removal found for AO-
SS than that for AO-H2O2 at 300 mA (see Figure 1).
3.4. Evolution of Aromatic Intermediates. Reversed-phase
chromatograms of electrolyzed solutions displayed a few
additional absorption peaks than that of atrazine. They were
analyzed to attempt to detect possible aromatic byproducts
coming from dealkylation, deamination, and/or hydroxylation
reactions under the action of hydroxyl radicals such as des-
ethylatrazine, desisopropylatrazine, desethyldesisopropylatrazine,
desethyldesisopropyl-2-hydroxyatrazine, and cyanuric acid.22,33
Among these derivatives, only the formation of desethylatrazine
(tr ) 3.1 min), desethyldesisopropylatrazine (tr ) 2.1 min), and
cyanuric acid (tr ) 1,8 min) was confirmed by this technique
Borràs et al.
Figure 5. Evolution of the main aromatic intermediates detected during
the degradation of 100 mL of a 30 mg L-1 atrazine solution in 0.05 M
Na2SO4 at pH 3.0 and 35 °C by means of (a) AO-SS, (b) EF, and (c)
PEF. Compounds: ([) desethylatrazine at 100 mA and cyanuric acid
at (]) 100, (0) 300, and (4) 450 mA.
from comparison of their retention times and UV-vis spectra,
measured on the diode array detector, with those of pure
compounds. The concentrations of these byproducts were then
determined via calibration with external standards.
Figure 5 illustrates the evolution of cyanuric acid for AO-
SS, EF, and PEF. This compound is the last and most persistent
aromatic byproduct detected in the degradation of atrazine by
AOPs because it cannot be directly destroyed by •OH.42-51
Polcaro et al.9 showed that cyanuric acid can be partially
removed in acid medium by AO-SS operating at 50 mA cm-2.
This behavior can also be observed in Figure 5a for this
technique at 100 mA (current density, 33 mA cm-2), where this
acid attains a maximum of 0.8 mg L-1 between 240 and 360
min, dropping to 0.4 mg L-1 at the end of electrolysis. In
contrast, it is completely removed in 180-300 min by this
EAOP operating at higher currents of 300 (current density, 100
mA cm-2) and 450 mA (current density, 150 mA cm-2), after
reaching maximum concentrations of 2.0 and 3.9 mg L-1,
respectively, at 60 min. The larger accumulation of cyanuric
acid as the current rises can be related to the faster destruction
of atrazine (see Figure 4b) and the precedent byproducts with
the higher amounts of BDD(•OH) produced from reaction 1.
When such species disappear at 300 and 450 mA, cyanuric acid
can be completely destroyed by BDD(•OH). Its presence at the
Degradation of Atrazine by EAOPs
Figure 6. Proposed reaction sequence for the degradation of atrazine to cyanuric acid by EAOPs with a BDD anode.
end of electrolysis at 100 mA is then indicative of a slower
removal of byproducts that are not completely converted into
cyanuric acid. This fact is corroborated from the EF and PEF
treatments at 100 mA. Thus, Figure 5b depicts a maximum of
4.6 mg L-1 of cyanuric acid at 90 min of EF, whereupon it
decays to disappear in 540 min. This behavior can be accounted
for by the parallel quicker destruction of atrazine (see Figure
4a) and the precedent byproducts with •OH formed from
Fenton’s reaction 4, accelerating the accumulation of cyanuric
acid that reacts slowly with BDD(•OH). This effect is less
significant in PEF, where the rapid photolysis of some byprod-
ucts with UVA light (probably Fe(III) complexes) leads to a
smaller accumulation of cyanuric acid, only 0.4 mg L-1 as the
maximum at 180 min, disappearing in 540 min, that is, the same
time as that in EF.
The different influence of oxidants and UVA light on the
degradation of atrazine can also be deduced from the evolution
of desethylatrazine working at 100 mA. This dealkylated
derivative was detected in very small contents (<0.1 mg L-1)
in AO-SS, as expected if it reacts with BDD(•OH) at the same
rate at which it is generated. In contrast, the quicker reaction
of atrazine with •OH in EF (see Figure 4a) causes an accumula-
tion of 1.4 mg L-1 of this compound at 90 min, further
disappearing in 240 min, as shown in Figure 5b. Additional
photolysis under UVA irradiation of the byproducts yielding
desethylatrazine increases its maximum to 2.9 mg L-1 in 60
min, reaching total removal in 180 min, as can be seen in Figure
5c. These findings, along with the behavior described above
for cyanuric acid, evidence the positive synergistic action of
•
OH and UVA light in PEF, yielding higher oxidation power
than AO-H2O2 and EF.
On the basis of detected intermediates, the reaction sequence
of Figure 6 is proposed for the main degradation pathway of
atrazine to cyanuric acid. Electrogenerated BDD(•OH) in AO,
along with •OH in EF and PEF, are assumed to be the main
oxidants in the consecutive conversion of the herbicide into
desethylatrazine, desethyldesisopropylatrazine, and cyanuric
acid. The positive action of UVA light for desethylatrazine
formation in PEF is also remarked. Dechlorination and deami-
nation lead to the release of Cl-, NO3-, and NH4+ ions, as
discussed in the subsection below.
3.5. Time Course of Generated Carboxylic Acids and
Released Inorganic Ions. Ion-exclusion chromatograms of
electrolyzed solutions of atrazine were recorded to detect and
J. Phys. Chem. A, Vol. 114, No. 24, 2010 6619
quantify generated carboxylic acids. However, no absorption
peaks were found in these chromatograms for AO-SS and AO-
H2O2 techniques. This is not surprising since BDD(•OH) is able
to destroy all short linear carboxylic acids at the same rate at
which they are produced because of the slow degradation of
aromatic intermediates.2,3 Nevertheless, ion-exclusion chromato-
grams obtained for the EF and PEF treatments displayed peaks
related to oxalic (tr ) 6.4 min), oxamic (tr ) 8.8 min), and
formic (tr ) 14.0 min) acids. Their detection can be explained
by the quicker reaction of aromatic byproducts with •OH
producing carboxylic acids that are accumulated since they are
more slowly removed with BDD(•OH) and •OH. Oxalic acid
(COOH-COOH) can be formed from the oxidation of ethyl
and isopropyl groups released during dealkylation reactions, for
example, the generation of desethylatrazine and desethyldesio-
sopropylatrazine (see Figure 6). Oxamic acid (COOH-
CO(NH2)) could result from the oxidation of the ethylamino
group released during deamination reactions. Formic acid
(HCOOH) can be produced from the oxidation of all carbon
atoms, including those proceeding from the cleavage of the
heteroaromatic ring.
As an example, Figure 7a and b shows the time course of
the above acids in EF and PEF at 100 mA, respectively. Formic
acid is largely accumulated, up to 10.6 mg L-1 at 120 min of
EF and 5.9 mg L-1 at 300 min of PEF, and practically removed
in 540 min. Overall destruction of oxalic and oxamic acid also
takes place at this time, although they are present in solution to
a much lesser extent with respective maxima of 1.26 and 0.19
mg L-1 in EF, decreasing to 0.13 and 0.06 mg L-1 in PEF. The
existence of lower concentrations of carboxylic acids in the latter
method confirms the synergistic effect of UVA light during the
degradation process of atrazine. Thus, the rapid decay of oxalic
acid in PEF can be accounted for by the fast photolysis of
Fe(III)-oxalate complexes (Fe(C2O4)+, Fe(C2O4)2-, and
Fe(C2O4)33-) as follows53
2Fe(C2O4)(3-2n)
n + hν f 2Fe2+ + (2n - 1)C2O2-
4 + 2CO2
(14)
Note that after 540 min at 100 mA, the persistent intermediates
detected such as cyanuric acid (see Figure 6) and carboxylic
acids (see Figure 7) have disappeared or exist in very small
content, while the solution TOC is only reduced by 85% in all
6620 J. Phys. Chem. A, Vol. 114, No. 24, 2010
Figure 7. Time course of the concentration of (]) formic, (O) oxalic,
and (0) oxamic acids during the treatment of 100 mL of a 30 mg L-1
atrazine solution in 0.05 M Na2SO4 of pH 3.0 by (a) EF and (b) PEF
at 100 mA and 35 °C.
EAOPs (see Figure 2a). That means that other undetected
byproducts still remain in the electrolyzed solutions, and their
content can only be reduced to 6-8% of the initial TOC
operating at higher currents (see Figure 2a).
Inorganic ions released during the EAOPs treatments under
optimum conditions of pH 3.0 at 300 mA for 540 min were
quantified by ionic chromatography. The initial chlorine of
atrazine is rapidly converted into Cl- ion, although Figure 8a
shows that this ion is unstable and disappears from the solution
in all methods, owing to its slow oxidation to Cl2 with
BDD(•OH).52 Moreover, a faster Cl- accumulation using EF
and PEF compared with that with AO-SS can be observed,
indicating the existence of more rapid dechlorination reactions
of aromatic intermediates with •OH. On the other hand, the initial
nitrogen of atrazine is progressively transformed into the NO3-
ion, as well as into the NH4+ ion to a much lesser extent. Figure
8b and c evidences that the evolution of both ions depends on
the EAOP applied. Similar concentrations for each ion are
accumulated in EF and PEF, with final values of ∼30.0 mg
L-1 for NO3- (68% of initial nitrogen) and 4.0 mg L-1 for NH4+
(32% of initial nitrogen), while lower contents of 17.3 mg L-1
for NO3- (40% of initial nitrogen) and 3.0 mg L-1 for NH4+
(24% of initial nitrogen) are determined at the end of AO-SS.
Since only 64% of the initial nitrogen is converted into inorganic
ions by the latter method, in front of 100% for EF and PEF,
one can infer that N-derivatives are completely mineralized with
BDD(•OH) and •OH as oxidants but partially decomposed with
BDD(•OH) alone, giving rise to byproducts that are released
from the medium, probably volatile NOx species, in AO
treatment.
4. Conclusions
It has been demonstrated that acidic aqueous solutions of
atrazine can be mineralized up to 94% as a maximum by EAOPs
with a BDD anode, indicating that they can be useful for the
Borràs et al.
Figure 8. Evolution of (a) chloride, (b) nitrate, and (c) ammonium
ions released during the degradation of 100 mL of a 30 mg L-1 atrazine
solution in 0.05 M Na2SO4 of pH 3.0 by (]) AO-SS, (b) EF, and (3)
PEF at 300 mA and 35 °C.
decontamination of wastewaters containing this herbicide. The
mineralization rate is limited by the oxidation of persistent
byproducts with BDD(•OH), although it is enhanced by parallel
electrochemical reduction of organics at the SS cathode or their
photolysis by UVA irradiation under the synergistic action of
•
OH in PEF. Optimum conditions of 300 mA and pH 3.0 have
been determined for the EAOPs treatments. PEF has higher
oxidation power than AO-H2O2 and EF but quite similar
degradation ability as AO-SS. Atrazine always follows a pseudo-
first-order decay. The most persistent aromatic derivative,
cyanuric acid, is completely removed in all methods by
BDD(•OH), except for AO at 100 mA due to the slow
destruction of precedent intermediates. Reversed-phase HPLC
revealed the formation of dealkylated aromatic byproducts such
as desethylatrazine and desethyldesisopropylatrazine. Short
linear carboxylic acids such as oxalic, oxamic, and formic were
detected by ion-exclusion HPLC in EF and PEF. The rapid
photolysis of Fe(III)-oxalate complexes explains the lower
accumulation of oxalic acid in the latter technique. The Cl-
ion lost in the degradation processes was completely removed
from the treated solutions. All initial nitrogen was transformed
into NO3- and NH4+ ions in EF and PEF but not in AO, where
36% of nitrogen was released from the solution probably as
volatile NOx species.
Degradation of Atrazine by EAOPs
Acknowledgment. Financial support from MEC (Ministerio
de Ciencia y Tecnologı́a, Spain) though Project CTQ2007-
60708/BQU, cofinanced with FEDER funds, is acknowledge.
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